JP5504614B2 - Negative electrode material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery using the negative electrode material - Google Patents
Negative electrode material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery using the negative electrode material Download PDFInfo
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- JP5504614B2 JP5504614B2 JP2008290277A JP2008290277A JP5504614B2 JP 5504614 B2 JP5504614 B2 JP 5504614B2 JP 2008290277 A JP2008290277 A JP 2008290277A JP 2008290277 A JP2008290277 A JP 2008290277A JP 5504614 B2 JP5504614 B2 JP 5504614B2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 35
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- -1 nitrogen-containing carbides Chemical class 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
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- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、リチウムイオン二次電池用負極材料とその製造方法、及び、その負極材料を用いたリチウムイオン二次電池に関するものである。 The present invention relates to a negative electrode material for a lithium ion secondary battery, a production method thereof, and a lithium ion secondary battery using the negative electrode material.
近年、電子機器の小型化および軽量化の要求に伴い、鉛蓄電池やニッケル・カドミウム電池に替わる高容量二次電池として、黒鉛を負極材料に用いたリチウムイオン二次電池が実用化されている。 In recent years, with the demand for downsizing and weight reduction of electronic devices, lithium ion secondary batteries using graphite as a negative electrode material have been put to practical use as high-capacity secondary batteries that replace lead-acid batteries and nickel-cadmium batteries.
しかしながら、このようなリチウムイオン二次電池には、初回の充放電時に、充電されたリチウムが完全に放電されないという問題があった。このような現象は、負極表面で電解液が電気分解されるためであると考えられた。このため、負極表面での電解液の電気分解反応を抑制することは、不可逆容量を小さくして電池特性を改善する一つの対策として有効である。また、このような対策は、リチウムイオン二次電池の負荷特性、充電特性、サイクル特性など、様々な電池特性を改善する方法としても有効である。 However, such a lithium ion secondary battery has a problem that the charged lithium is not completely discharged during the first charge / discharge. Such a phenomenon was considered to be due to electrolysis of the electrolyte solution on the negative electrode surface. For this reason, suppressing the electrolytic reaction of the electrolytic solution on the negative electrode surface is effective as one measure for reducing the irreversible capacity and improving the battery characteristics. Such a countermeasure is also effective as a method for improving various battery characteristics such as load characteristics, charging characteristics, and cycle characteristics of the lithium ion secondary battery.
これまで、本発明者らは、負極表面での電解液の電気分解反応を抑制して、不可逆容量を小さくするために、電解液との反応性の低い低結晶性炭素で表面を被覆した黒鉛を用いた負極材料を開示している（例えば、特許文献１参照）。 In the past, the present inventors have been able to suppress the electrolysis reaction of the electrolyte solution on the negative electrode surface and reduce the irreversible capacity, so that the graphite coated on the surface with low crystalline carbon having low reactivity with the electrolyte solution. Discloses a negative electrode material using, for example, Patent Document 1.
具体的には、黒鉛粒子（１）の表面に、ポリエチレンまたはポリスチレンの粒子（２）の熱分解成分による被覆層が形成された複合粒子からなることを特徴とするリチウムイオン二次電池用負極材料を開示している。
しかしながら、近年、自動車や工具等への用途として、従来よりも一層急速に充放電できるリチウムイオン二次電池が求められており、さらなる性能向上が求められている。 However, in recent years, lithium ion secondary batteries that can be charged and discharged more rapidly than before have been demanded for use in automobiles and tools, and further performance improvements have been demanded.
本発明は上記事情に鑑みてなされたものであり、負極表面での電解液の電気分解反応をより一層抑制することのできる負極材料とその製造方法を提供することを目的とする。 This invention is made | formed in view of the said situation, and it aims at providing the negative electrode material which can suppress further the electrolysis reaction of the electrolyte solution on the negative electrode surface, and its manufacturing method.
上記課題を解決することができた本発明のリチウムイオン二次電池用負極材料は、窒素含有材料の炭化物による被覆層が黒鉛粒子の表面に形成された複合粒子を含有することを特徴とする。このように、黒鉛粒子の表面に窒素含有材料の炭化物による被覆層が形成された複合粒子を負極材料として用いることにより、負極表面と電解液との電気分解反応をより一層抑制することができる。また、複合粒子中における炭化物の含有率を減らしても、負極表面と電解液との反応性を十分に低くすることができる。さらに、負極表面が若干親水性になることから、負極表面と電解液との濡れ性が向上する。 The negative electrode material for a lithium ion secondary battery of the present invention that has solved the above-mentioned problems is characterized by containing composite particles in which a coating layer made of a carbide of a nitrogen-containing material is formed on the surface of graphite particles. Thus, the electrolysis reaction between the negative electrode surface and the electrolytic solution can be further suppressed by using, as the negative electrode material, composite particles in which the coating layer of the nitrogen-containing material is formed on the surface of the graphite particles. Moreover, even if the carbide content in the composite particles is reduced, the reactivity between the negative electrode surface and the electrolytic solution can be sufficiently lowered. Furthermore, since the negative electrode surface becomes slightly hydrophilic, the wettability between the negative electrode surface and the electrolytic solution is improved.
本発明のリチウムイオン二次電池用負極材料において、前記黒鉛粒子と前記窒素含有材料との混合比が９９．５／０．５〜７０／３０（質量比）であることが、好ましい実施態様である。 In the negative electrode material for a lithium ion secondary battery of the present invention, it is preferable that the mixing ratio of the graphite particles and the nitrogen-containing material is 99.5 / 0.5 to 70/30 (mass ratio). is there.
また、前記窒素含有材料が、尿素、ウレタン樹脂、尿素樹脂、及びＡＢＳ樹脂よりなる群から選択される少なくとも１種であることが好ましい実施態様である。 In another preferred embodiment, the nitrogen-containing material is at least one selected from the group consisting of urea, urethane resin, urea resin, and ABS resin.
本発明には、上記負極材料を用いたことを特徴とするリチウムイオン二次電池が包含される。 The present invention includes a lithium ion secondary battery using the above negative electrode material.
さらに、尿素、ウレタン樹脂、尿素樹脂、及びＡＢＳ樹脂よりなる群から選択される少なくとも１種の窒素含有材料と黒鉛粒子とを物理的に混合し、不活性ガス雰囲気中５００℃〜２０００℃で熱処理して、前記窒素含有材料の炭化物による被覆層が前記黒鉛粒子の表面に形成された複合粒子を得ることを特徴とするリチウムイオン二次電池用負極材料の製造方法も、本発明に包含される。 Further, at least one nitrogen-containing material selected from the group consisting of urea, urethane resin, urea resin, and ABS resin and graphite particles are physically mixed and heat treated at 500 ° C. to 2000 ° C. in an inert gas atmosphere. A method for producing a negative electrode material for a lithium ion secondary battery is also included in the present invention, wherein composite particles in which a coating layer of a carbide of the nitrogen-containing material is formed on the surface of the graphite particles are obtained. .
本発明のリチウムイオン二次電池用負極材料の製造方法において、前記黒鉛粒子と前記窒素含有材料との混合比が９９．５／０．５〜７０／３０（質量比）であることが、好ましい態様である。 In the method for producing a negative electrode material for a lithium ion secondary battery of the present invention, the mixing ratio of the graphite particles and the nitrogen-containing material is preferably 99.5 / 0.5 to 70/30 (mass ratio). It is an aspect.
本発明によれば、電解液の電気分解反応をより一層抑制することができるリチウムイオン二次電池用負極材料を得ることができた。 According to the present invention, a negative electrode material for a lithium ion secondary battery that can further suppress the electrolytic reaction of the electrolytic solution can be obtained.
＜リチウムイオン二次電池用負極材料＞
本発明のリチウムイオン二次電池用負極材料は、窒素含有材料の炭化物による被覆層が黒鉛粒子の表面に形成された複合粒子を含有することを特徴とする。以下、本発明の負極材料について詳細に説明する。
<Anode material for lithium ion secondary battery>
The negative electrode material for a lithium ion secondary battery according to the present invention is characterized in that it includes composite particles in which a coating layer made of a carbide of a nitrogen-containing material is formed on the surface of graphite particles. Hereinafter, the negative electrode material of the present invention will be described in detail.
（被覆層）
本発明の複合粒子は、黒鉛粒子の表面に窒素含有材料の炭化物による被覆層が形成されてなることから、この複合粒子から得られる負極の表面と電解液との電気分解反応をより一層抑制することができる。また、黒鉛粒子に対する窒素含有材料の配合量を減らして被覆層を形成しても、負極表面と電解液との反応を十分に抑制することができる。その結果、複合粒子中の黒鉛粒子の含有率を高くすることができるため、これを用いて得られる電池の容量を大きくすることができる。また、負極表面と電解液との濡れ性が向上することから、電池の容量をさらに向上させることができる。
(Coating layer)
Since the composite particle of the present invention has a coating layer formed of a carbide of a nitrogen-containing material on the surface of the graphite particle, the electrolytic reaction between the surface of the negative electrode obtained from the composite particle and the electrolytic solution is further suppressed. be able to. Moreover, even if the coating amount is formed by reducing the blending amount of the nitrogen-containing material with respect to the graphite particles, the reaction between the negative electrode surface and the electrolytic solution can be sufficiently suppressed. As a result, since the content of the graphite particles in the composite particles can be increased, the capacity of the battery obtained using this can be increased. Moreover, since the wettability between the negative electrode surface and the electrolytic solution is improved, the capacity of the battery can be further improved.
本発明の複合粒子における被覆層は、黒鉛粒子と窒素含有材料とを９９．５／０．５〜７０／３０（質量比）で混合して形成されることが好ましく、かかる混合比は、より好ましくは９９／１〜８０／２０（質量比）、さらに好ましくは９８／２〜８５／１５（質量比）である。黒鉛粒子と窒素含有材料との混合比が上記範囲にあることにより、黒鉛粒子の活性の高いサイト（特にエッジ面）を窒素含有材料の炭化物（より詳細には、窒素含有官能基）で被覆することができるため、これを負極材料として用いた際に、負極表面と電解液との反応を十分に抑制することができる。また、粒子としての嵩密度が向上するため、これを負極材料として用いた際には、黒鉛としてのすぐれた特性は維持したまま電解液との反応性が低くなって、不可逆容量の小さい、かつ初期効率、負荷特性、充電特性、及びサイクル特性にすぐれた負極極板を得ることができる。 The coating layer in the composite particles of the present invention is preferably formed by mixing graphite particles and a nitrogen-containing material at 99.5 / 0.5 to 70/30 (mass ratio). Preferably it is 99 / 1-80 / 20 (mass ratio), More preferably, it is 98 / 2-85 / 15 (mass ratio). When the mixing ratio of the graphite particles and the nitrogen-containing material is within the above range, the highly active sites (particularly the edge surface) of the graphite particles are coated with the carbide of the nitrogen-containing material (more specifically, the nitrogen-containing functional group). Therefore, when this is used as the negative electrode material, the reaction between the negative electrode surface and the electrolytic solution can be sufficiently suppressed. Further, since the bulk density as particles is improved, when this is used as a negative electrode material, the reactivity with the electrolyte solution is reduced while maintaining excellent characteristics as graphite, and the irreversible capacity is small. A negative electrode plate excellent in initial efficiency, load characteristics, charging characteristics, and cycle characteristics can be obtained.
黒鉛粒子に対する窒素含有材料の混合比が９９．５／０．５より高い場合には、黒鉛粒子表面への被覆層の形成が不充分となるため、本発明の複合粒子を用いて得られる負極の表面と電解液との反応を十分に抑制することができない場合がある。また、黒鉛粒子に対する窒素含有材料の混合比が７０／３０未満の場合には、複合粒子中の、高容量／高エネルギー密度に寄与する黒鉛粒子の含有率が低くなるため、これを用いて得られる電池の容量を大きくできない場合がある。 When the mixing ratio of the nitrogen-containing material to the graphite particles is higher than 99.5 / 0.5, the formation of a coating layer on the surface of the graphite particles becomes insufficient, so that the negative electrode obtained using the composite particles of the present invention In some cases, the reaction between the surface and the electrolyte solution cannot be sufficiently suppressed. In addition, when the mixing ratio of the nitrogen-containing material to the graphite particles is less than 70/30, the content of the graphite particles contributing to high capacity / high energy density in the composite particles is low. Battery capacity may not be increased.
本発明で用いる窒素含有材料は、尿素や、ウレタン樹脂（例えば、エーテル系ポリウレタンやエステル系ポリウレタン等）、尿素樹脂、ＡＢＳ樹脂等であることが好ましい。これらの窒素含有材料は、単独で用いても、２種以上を組み合わせて用いてもよい。なお、本発明の窒素含有材料には、含窒素環化合物（例えば、ポリビニルピロリドン）やイミド樹脂は含まない。 The nitrogen-containing material used in the present invention is preferably urea, urethane resin (for example, ether polyurethane or ester polyurethane), urea resin, ABS resin or the like. These nitrogen-containing materials may be used alone or in combination of two or more. The nitrogen-containing material of the present invention does not contain a nitrogen-containing ring compound (for example, polyvinyl pyrrolidone) or an imide resin.
本発明で用いる窒素含有材料は、粒子であることが好ましい。これは、本発明の複合粒子から得られる負極材料と電解液との反応抑制効果や、負極材料を製造する際の経済性の観点から最適であるからである。 The nitrogen-containing material used in the present invention is preferably particles. This is because it is optimal from the viewpoint of suppressing the reaction between the negative electrode material obtained from the composite particles of the present invention and the electrolytic solution and the economical efficiency in producing the negative electrode material.
本発明で用いる窒素含有材料の粒子の平均粒子径は、０．１μｍ以上が好ましく、１μｍ以上がより好ましく、２０ｍｍ以下が好ましく、１０ｍｍ以下がより好ましい。粒子径がこのような範囲にある窒素含有材料を用いることにより、黒鉛粒子との混合効率を高めることができる。 The average particle diameter of the particles of the nitrogen-containing material used in the present invention is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 20 mm or less, and more preferably 10 mm or less. By using a nitrogen-containing material having a particle diameter in such a range, the mixing efficiency with the graphite particles can be increased.
本発明で用いる窒素含有材料の粒子の粒子径は、例えば、窒素含有材料としてウレタン樹脂を用いる場合には、レーザー回折式粒度分布測定装置を用いて測定されるメジアン径（Ｄ５０）が１μｍ以上であることが好ましく、１０μｍ以上であることがより好ましく、１０ｍｍ以下であることが好ましく、５ｍｍ以下であることがより好ましい。また、窒素含有材料として尿素を用いる場合には、光学顕微鏡や電子顕微鏡を用いて任意の尿素粒子１００個を測定したときの粒子径の範囲が１μｍ〜５ｍｍであることが好ましく、５μｍ〜１ｍｍであることがより好ましい。また、窒素含有材料としてＡＢＳ樹脂を用いる場合には、ノギスや光学顕微鏡や電子顕微鏡により任意のＡＢＳ樹脂粒子３０個を測定したときの平均粒子径が１μｍ以上であることが好ましく、５μｍ以上であることがより好ましく、２０ｍｍ以下であることが好ましく、１０ｍｍ以下であることがより好ましい。 The particle diameter of the nitrogen-containing material particles used in the present invention is, for example, when a urethane resin is used as the nitrogen-containing material, the median diameter (D50) measured using a laser diffraction particle size distribution measuring device is 1 μm or more. It is preferably 10 μm or more, more preferably 10 mm or less, and even more preferably 5 mm or less. Moreover, when using urea as a nitrogen-containing material, it is preferable that the range of the particle diameter when measuring 100 arbitrary urea particles using an optical microscope or an electron microscope is 1 μm to 5 mm, and 5 μm to 1 mm. More preferably. When an ABS resin is used as the nitrogen-containing material, the average particle diameter when measuring 30 arbitrary ABS resin particles with a caliper, an optical microscope, or an electron microscope is preferably 1 μm or more, and preferably 5 μm or more. More preferably, it is preferably 20 mm or less, and more preferably 10 mm or less.
（黒鉛粒子）
本発明で用いる黒鉛粒子としては、天然黒鉛または人造黒鉛が挙げられる。これらは、適当な方法で粉砕したものであってもよく、球形化などの改質を行ったものであってもよい。球形化改質の例は、本出願人の出願にかかる特開平１１−２６３６１２号公報に開示されている。また、黒鉛粒子のメジアン径（Ｄ５０）は、特に限定されるものではないが、１μｍ以上が好ましく、１０μｍ以上がより好ましく、６０μｍ以下が好ましく、５０μｍ以下がより好ましい。
(Graphite particles)
Examples of the graphite particles used in the present invention include natural graphite and artificial graphite. These may be pulverized by an appropriate method or may be subjected to modification such as spheroidization. An example of spheroidization modification is disclosed in Japanese Patent Application Laid-Open No. 11-263612, which is filed by the present applicant. The median diameter (D50) of the graphite particles is not particularly limited, but is preferably 1 μm or more, more preferably 10 μm or more, preferably 60 μm or less, and more preferably 50 μm or less.
（複合粒子の含有率）
本発明のリチウムイオン二次電池用負極材料には、上記複合粒子が好ましくは５０質量％以上含まれることが好ましく、８０質量％以上含まれることが好ましく、１００質量％含まれることが最も好ましい。複合粒子の含有率が５０質量％未満の場合には、負極表面と電解液との反応を十分に抑制することができない場合がある。
(Content of composite particles)
In the negative electrode material for a lithium ion secondary battery of the present invention, the composite particles are preferably contained in an amount of 50% by mass or more, preferably 80% by mass or more, and most preferably 100% by mass. When the content of the composite particles is less than 50% by mass, the reaction between the negative electrode surface and the electrolytic solution may not be sufficiently suppressed.
（他の成分）
本発明のリチウムイオン二次電池用負極材料には、上記複合粒子以外の他の成分が含まれてもよい。他の成分としては、例えば上記黒鉛粒子や導電剤等が挙げられる。
(Other ingredients)
The negative electrode material for a lithium ion secondary battery of the present invention may contain components other than the composite particles. Examples of other components include the above graphite particles and conductive agents.
＜リチウムイオン二次電池用負極材料の製造方法＞
（複合粒子の製造方法）
本発明の複合粒子は、黒鉛粒子と窒素含有材料とを物理的に混合し、不活性ガス雰囲気中５００℃〜２０００℃で熱処理して、窒素含有材料の炭化物による被覆層を黒鉛粒子の表面に形成することによって製造される。黒鉛粒子と窒素含有材料との混合比は、上記の通りである。
<Method for producing negative electrode material for lithium ion secondary battery>
(Method for producing composite particles)
The composite particles of the present invention are obtained by physically mixing graphite particles and a nitrogen-containing material, heat-treating them in an inert gas atmosphere at 500 ° C. to 2000 ° C., and forming a coating layer made of carbide of the nitrogen-containing material on the surface of the graphite particles. Manufactured by forming. The mixing ratio of the graphite particles and the nitrogen-containing material is as described above.
黒鉛粒子と窒素含有材料とを物理的に混合して得られる混合物の熱処理は、５００℃以上で行われることが好ましく、６００℃以上で行われることがより好ましく、２０００℃以下で行われることが好ましく、１３００℃以下で行われることがより好ましい。上記温度範囲で熱処理することにより、昇温の過程で生成した窒素含有材料の分解成分は、気相で黒鉛粒子の隅々にまで拡散し、黒鉛表面の活性な部分と反応して添着し、薄くて均一な被膜層を形成する。そしてこれをさらに熱処理することにより、被膜層は炭化し、安定な被覆層を形成する。 The heat treatment of the mixture obtained by physically mixing the graphite particles and the nitrogen-containing material is preferably performed at 500 ° C. or more, more preferably at 600 ° C. or more, and at 2000 ° C. or less. Preferably, it is carried out at 1300 ° C. or lower. By performing the heat treatment in the above temperature range, the decomposition component of the nitrogen-containing material generated in the temperature rising process diffuses to every corner of the graphite particles in the gas phase, reacts with and adheres to the active part of the graphite surface, A thin and uniform coating layer is formed. And when this is further heat-treated, the coating layer is carbonized to form a stable coating layer.
上記熱処理が５００℃未満で行われる場合には、窒素含有材料の炭化物による黒鉛粒子上への被覆層の形成が不充分となる場合がある。また、熱処理が２０００℃を超える温度で行われる場合には、設備面および所要電力の点で不利となる。 When the heat treatment is performed at less than 500 ° C., the formation of a coating layer on the graphite particles by the carbide of the nitrogen-containing material may be insufficient. In addition, when the heat treatment is performed at a temperature exceeding 2000 ° C., it is disadvantageous in terms of equipment and required power.
上記の熱処理は、Ｎ２、Ａｒ、Ｈｅ、ＣＯ２等の不活性ガス雰囲気中で行う。この際、密閉雰囲気中で行うことが好ましい。これにより、窒素含有材料の熱分解により生じた熱分解成分が滞留して、黒鉛粒子の表面を被覆し易くなる。 The above heat treatment is carried out in N 2, Ar, He, an inert gas atmosphere such as CO 2. At this time, it is preferably performed in a sealed atmosphere. Thereby, the thermal decomposition component generated by the thermal decomposition of the nitrogen-containing material stays, and the surface of the graphite particles is easily covered.
（リチウムイオン二次電池用負極材料）
本発明の複合粒子は、例えば、これにポリフッ化ビニリデンなどのバインダーと、Ｎ−メチルピロリドンなどの溶剤とを加えてスラリーとし、銅箔等の金属製の集電体の基板にこのスラリーを塗布して乾燥することにより、リチウムイオン二次電池用の負極とすることができる。
(Anode material for lithium ion secondary battery)
The composite particles of the present invention are made, for example, by adding a binder such as polyvinylidene fluoride and a solvent such as N-methylpyrrolidone to the slurry, and applying the slurry to a substrate of a metal current collector such as a copper foil. And it can be set as the negative electrode for lithium ion secondary batteries by drying.
＜リチウムイオン二次電池＞
本発明のリチウムイオン二次電池に用いる正極材料としては、特に限定されるものではなく、改質ＭｎＯ2、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＮｉ1-yＣｏyＯ2、ＬｉＭｎＯ2、ＬｉＭｎ2Ｏ4、ＬｉＦｅＯ2などが用いられる。電解液としては、エチレンカーボネートなどの有機溶媒や、この有機溶媒とジメチルカーボネート、ジエチルカーボネート、１，２−ジメトキシエタン、１，２−ジエトキシメタン、エトキシメトキシエタンなどの低沸点溶媒との混合溶媒に、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3などの電解液溶質を溶解した溶液が用いられる。セパレーターについても、特に限定されるものではなく、公知の材料を適宜用いることができる。
<Lithium ion secondary battery>
The positive electrode material used for the lithium ion secondary battery of the present invention is not particularly limited, and is modified MnO 2 , LiCoO 2 , LiNiO 2 , LiNi 1-y Co y O 2 , LiMnO 2 , LiMn 2 O 4. LiFeO 2 or the like is used. As an electrolytic solution, an organic solvent such as ethylene carbonate, or a mixed solvent of this organic solvent and a low boiling point solvent such as dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxymethane, ethoxymethoxyethane, etc. In addition, a solution in which an electrolyte solute such as LiPF 6 , LiBF 4 , LiClO 4 , or LiCF 3 SO 3 is dissolved is used. The separator is not particularly limited, and a known material can be appropriately used.
以下、本発明を実施例によって詳細に説明するが、本発明は、下記実施例によって限定されるものではなく、本発明の趣旨を逸脱しない範囲の変更、実施の態様は、いずれも本発明の範囲内に含まれる。なお下記実施例および比較例において「部」、「％」とあるのは、それぞれ質量部、質量％を意味する。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples, and all modifications and embodiments without departing from the gist of the present invention are not limited thereto. Included in range. In the following examples and comparative examples, “parts” and “%” mean parts by mass and mass%, respectively.
先ず、実施例および比較例で用いた測定方法、及び評価方法について、以下説明する。 First, measurement methods and evaluation methods used in Examples and Comparative Examples will be described below.
（黒鉛粒子の平均粒子径の測定）
株式会社島津製作所製のレーザー回折式粒度分布測定装置ＳＡＬＤ−２０００を用いて測定を行い、体積基準メジアン径（Ｄ５０）を求めた。
(Measurement of average particle diameter of graphite particles)
Measurement was performed using a laser diffraction particle size distribution analyzer SALD-2000 manufactured by Shimadzu Corporation, and a volume-based median diameter (D50) was obtained.
（窒素含有材料の粒子径の測定）
実施例１で用いたウレタン樹脂については、株式会社島津製作所製のレーザー回折式粒度分布測定装置ＳＡＬＤ−２０００を用いて測定を行い、体積基準メジアン径（Ｄ５０）を求めた。
(Measurement of particle diameter of nitrogen-containing material)
The urethane resin used in Example 1 was measured using a laser diffraction particle size distribution analyzer SALD-2000 manufactured by Shimadzu Corporation, and a volume-based median diameter (D50) was obtained.
実施例２で用いた尿素については、光学顕微鏡を用いて任意の１００個の尿素粒子の粒子径を測定し、その範囲を求めた。 Regarding urea used in Example 2, the particle diameter of 100 arbitrary urea particles was measured using an optical microscope, and the range was determined.
他の実施例及び比較例で用いた窒素含有材料については、任意の３０個の窒素含有材料の粒子径をノギスにより測定し、その平均を求めた。 For the nitrogen-containing materials used in other examples and comparative examples, the particle diameters of any 30 nitrogen-containing materials were measured with calipers, and the average was obtained.
＜電極性能の評価＞
（初期効率）
負極材料（複合粒子）１００質量部と、バインダーとしてのポリフッ化ビニリデン３質量部と、溶剤としてのＮ−メチルピロリドンの適量とを混合し、液相で均一に撹拌した。得られたスラリーを銅箔上に塗布し、乾燥後、プレス機により加圧成形し、負極極板を作成してから、１５０℃で６時間真空乾燥を行った。リチウム箔をステンレス板に圧着したものをセパレーターを介して対極とし、２極式セルを組み立てた。組み立ては、水分値２０ｐｐｍ以下に調整したドライボックス内で行い、電解液としては、エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）との容積比１：１の混合溶媒にＬｉＰＦ6を１Ｍの割合で溶解したものを用いた。
<Evaluation of electrode performance>
(Initial efficiency)
100 parts by mass of a negative electrode material (composite particles), 3 parts by mass of polyvinylidene fluoride as a binder, and an appropriate amount of N-methylpyrrolidone as a solvent were mixed and stirred uniformly in a liquid phase. The obtained slurry was applied onto a copper foil, dried, and then pressure-formed with a press machine to prepare a negative electrode plate, followed by vacuum drying at 150 ° C. for 6 hours. A bipolar electrode was assembled by bonding a lithium foil to a stainless steel plate as a counter electrode through a separator. The assembly is performed in a dry box adjusted to a moisture value of 20 ppm or less. As an electrolyte, LiPF 6 is mixed at a ratio of 1M in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1. The dissolved one was used.
充電は、０．４２４ｍＡ／ｃｍ2（０．２Ｃ）の定電流値で７ｍＶになるまで充電した後、７ｍＶの定電位で電流値が０．０４２５ｍＡ／ｃｍ2となるまで行った。放電は、０．４２４ｍＡ／ｃｍ2の電流値で２．０Ｖになるまで行った。各サンプルの１回目の充電容量と放電容量とにより、
初期効率（％）＝１００×放電容量／充電容量を計算した。
Charging was performed until a constant current value of 0.424 mA / cm 2 (0.2 C) reached 7 mV, and then at a constant potential of 7 mV until the current value became 0.0425 mA / cm 2 . Discharging was performed until the voltage reached 2.0 V at a current value of 0.424 mA / cm 2 . By the first charge capacity and discharge capacity of each sample,
Initial efficiency (%) = 100 × discharge capacity / charge capacity was calculated.
（出力特性）
５０％充電時において、２．１２ｍＡ／ｃｍ2（１Ｃ）、６．３６ｍＡ／ｃｍ2（３Ｃ）、１０．６ｍＡ／ｃｍ2（５Ｃ）にて１０秒間放電後の電圧と放電電流との関係から単位電圧あたりの出力電流を算出することにより求めた。
(Output characteristics)
From the relationship between the voltage and discharge current after 10 seconds of discharge at 2.12 mA / cm 2 (1C), 6.36 mA / cm 2 (3C), 10.6 mA / cm 2 (5C) at 50% charge It was determined by calculating the output current per unit voltage.
（実施例１）
メジアン径（Ｄ５０）１２μｍの球状天然黒鉛２７０ｇに、メジアン径（Ｄ５０）２００μｍのウレタン樹脂粒子（出光テクノファイン株式会社製ウレタンパウダー）３０ｇを添加後、撹拌混合（粒子同士で物理的に混合）し、次いで窒素雰囲気下８００℃にて２時間熱処理を行った。この熱処理により、黒鉛粒子の表面に、ウレタン樹脂の炭化物による被覆層が形成された複合粒子を得た。
Example 1
After adding 30 g of urethane resin particles (urethane powder manufactured by Idemitsu Techno Fine Co., Ltd.) having a median diameter (D50) of 200 μm to 270 g of spherical natural graphite having a median diameter (D50) of 12 μm, the mixture is stirred and mixed (physically mixed between particles). Then, heat treatment was performed at 800 ° C. for 2 hours under a nitrogen atmosphere. By this heat treatment, composite particles in which a coating layer of urethane resin carbide was formed on the surface of the graphite particles were obtained.
（実施例２）
メジアン径（Ｄ５０）１２μｍの球状天然黒鉛２９１ｇに、粒子径１０μｍ〜５００μｍの尿素粒子（キシダ化学株式会社製尿素）９ｇを添加後、撹拌混合し、窒素雰囲気下８００℃にて２時間熱処理を行った。この熱処理により、黒鉛粒子の表面に、尿素の炭化物による被覆層が形成された複合粒子を得た。
(Example 2)
To 291 g of spherical natural graphite with a median diameter (D50) of 12 μm, 9 g of urea particles (urea manufactured by Kishida Chemical Co., Ltd.) with a particle diameter of 10 μm to 500 μm are added, mixed with stirring, and heat-treated at 800 ° C. for 2 hours in a nitrogen atmosphere. It was. By this heat treatment, composite particles in which a coating layer of urea carbide was formed on the surface of the graphite particles were obtained.
（実施例３）
メジアン径（Ｄ５０）１２μｍの球状天然黒鉛２９１ｇに、平均粒子径２ｍｍのＡＢＳ樹脂粒子（株式会社サンプラテック製ＡＢＳ樹脂）９ｇを添加後、撹拌混合し、窒素雰囲気下８００℃にて２時間熱処理を行った。この熱処理により、黒鉛粒子の表面に、ＡＢＳ樹脂の炭化物による被覆層が形成された複合粒子を得た。
(Example 3)
After adding 9 g of ABS resin particles (ABS resin manufactured by Sun Platec Co., Ltd.) having an average particle diameter of 2 mm to 291 g of spherical natural graphite having a median diameter (D50) of 12 μm, the mixture is stirred and mixed, and heat-treated at 800 ° C. for 2 hours in a nitrogen atmosphere. It was. By this heat treatment, composite particles in which a coating layer of carbide of ABS resin was formed on the surface of the graphite particles were obtained.
（比較例１）
メジアン径（Ｄ５０）１２μｍの球状天然黒鉛２７０ｇに、平均粒子径１ｍｍのポリスチレン粒子（キシダ化学株式会社製スチレンポリマー）３０ｇを添加後、撹拌混合し、窒素雰囲気下８００℃にて２時間熱処理を行った。この熱処理により、黒鉛粒子の表面に、ポリスチレンの炭化物による被覆層が形成された複合粒子を得た。
(Comparative Example 1)
30 g of polystyrene particles (styrene polymer manufactured by Kishida Chemical Co., Ltd.) with an average particle diameter of 1 mm are added to 270 g of spherical natural graphite with a median diameter (D50) of 12 μm, followed by stirring and mixing, followed by heat treatment at 800 ° C. for 2 hours in a nitrogen atmosphere. It was. By this heat treatment, composite particles in which a coating layer of polystyrene carbide was formed on the surface of the graphite particles were obtained.
（比較例２）
実施例１で用いた球状天然黒鉛を、窒素含有材料を用いたコート処理をすることなく、そのまま複合粒子として用いた。
(Comparative Example 2)
The spherical natural graphite used in Example 1 was used as composite particles as it was without being coated with a nitrogen-containing material.
実施例、及び比較例で得られた複合粒子を用いてリチウムイオン二次電池を作製し、初期効率と出力特性を求めた。結果を表１に示す。 Lithium ion secondary batteries were fabricated using the composite particles obtained in the examples and comparative examples, and the initial efficiency and output characteristics were determined. The results are shown in Table 1.
表１から、本発明の複合粒子を用いて得られるリチウムイオン二次電池は、ポリスチレン粒子の炭化物による被覆層が黒鉛粒子の表面に形成された複合粒子（比較例１）、及び黒鉛粒子（比較例２）を用いて得られるリチウムイオン二次電池に比して初期効率に優れること、すなわち、電解液と負極表面との反応がより一層抑制されていることがわかる。 From Table 1, the lithium ion secondary battery obtained by using the composite particles of the present invention is composed of composite particles (Comparative Example 1) in which a coating layer of carbide of polystyrene particles is formed on the surface of graphite particles, and graphite particles (Comparison) It can be seen that the initial efficiency is superior to the lithium ion secondary battery obtained using Example 2), that is, the reaction between the electrolytic solution and the negative electrode surface is further suppressed.
また、本発明の複合粒子を用いて得られるリチウムイオン二次電池は、出力特性にも優れていることから、高出力を必要とする用途、例えば、車載用途や工具用途に適用することができる。 In addition, since the lithium ion secondary battery obtained using the composite particles of the present invention is excellent in output characteristics, it can be applied to uses requiring high output, for example, in-vehicle use and tool use. .
本発明のリチウムイオン二次電池は、不可逆容量が小さく、また、負荷特性、充電特性、サイクル特性など、様々な電池特性に優れているため、自動車や工具等、従来よりも一層急速に充放電できる性能が求められる用途に好適に用いることができる。 The lithium ion secondary battery of the present invention has a small irreversible capacity and is excellent in various battery characteristics such as load characteristics, charging characteristics, and cycle characteristics. It can be suitably used for applications that require high performance.
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| JP5886875B2 (en) * | 2010-12-31 | 2016-03-16 | エギョン ペトロケミカル カンパニー リミテッドＡｅｋｙｕｎｇ Ｐｅｔｒｏｃｈｅｍｉｃａｌ Ｃｏ．， Ｌｔｄ． | Negative electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery using the same |
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